Nitrohydroxyethers



nited States 3,402,206 NITROHYDROXYETHERS atent John A. Frump, TerreHaute, Ind., assignor to Commercial Solvents Corporation, New York,N.Y., a corporation of Maryland No Drawing. Continuation-impart ofapplication Ser. No. 588,749, Oct. 24, 1966. This application Oct. 30,1967, Ser. No. 679,214

2 Claims. (Cl. 260615) ABSTRACT OF THE DISCLOSURE Nitrohydroxyethers ofthe formula wherein R is a member selected from the group consisting ofmethyl and hydrogen; wherein R is a member selected from the groupconsisting of alkyl radicals, for instance, of about 1 to 10 or 20carbon atoms, including lower alkyl radicals; lower hydroxyalkylradicals, for instance, of up to 5 carbon atoms; and a radical havingthe formula --(CH R wherein R in the above formula and radical isselected from the group consisting of wherein R R R R x and y have thevalues assigned them above which are useful as corrosion inhibitors,bactericides, pigment wetting and dispersing agents, emulsifiers andintermediates in the preparation of non-ionic surface active agents.Exemplary of such aminohydroxyethers is2-methyl-6-hydroxy-4-oxa-6-chloromethyl-2- hexylamine.

Cross reference to related applications This application is acontinuation-in-part of copending application Ser. No. 588,749, filedOct. 24, 1966- and now abandoned. Application Ser. No. 588,749 is adivision of application Ser. No. 302,470, filed Aug. 15, 1963, and nowU.S. Patent No. 3,296,313. Application Ser. No. 302,470 is acontinu-ation-in-part of abandoned application Ser. No. 8,234, filedFebruary 12, 1960.

Summary of the invention My invention relates to a new group of nitrogencompounds and a process for their preparation. More par- Patented Sept.17, 1968 ticularly, it relates to a catalytic process for oxyalkylatingnitroalcohols and nitropolyols with epoxides and the novel nitro andamino-hydroxyethers obtained thereby.

The novel nitrohydroxyethers, compounds A, of the invention are thosehaving the following general formula:

1 i([3--(CHR4)x-R2 wherein R. is a member selected from the groupconsisting of methyl and hydrogen; wherein R is a member selected fromthe group consisting of alkyl radicals, for instance, of about 1 to 10'or 20 carbon atoms including lower alkyl radicals; lower hydroxyalkylradicals, for instance, of up to 5 carbon atoms; and a radical havingthe general formula: -(CH --R wherein R in the above formula and radicalis a member selected from the group consisting of the radicals wherein Ris a member selected from the group consistin g of hydrogen, phenyl,nitro-substituted phenyl, halosubstituted phenyl, alkyl,hydroxyl-substituted alkyl, halosubstituted alkyl, alkene, andphenyl-substituted alkyl radicals; y is an integer ranging from about 1to 10 or 20 and x in the above formula and radical is an integer rangingfrom about 1 to 20.

The novel nitro compounds of my invention can be prepared 'by contactingan epoxide with a nitroalcohol having the formula:

Detailed description In the process for producing my new nitrocompounds, I generally employ temperatures ranging from about 0 C. toabout 150 C. At temperatures above 150 C. decomposition of the newcompounds may occur. Temperatures below 0 0, even though allowingformation of my new compounds, would not be economically practical dueto the requirement for expensive cooling equipment. While a broadtemperature range of from about 25 C. to about 150 C., for instance, issuitable for my process, I prefer to use temperatures ranging from about60 C. or C. to about C. When temperatures below the melting points ofthe nitroalcohols used in my invention are utilized, I prefer to use asolvent for the nitroalcohol Satisfactory results can be obtained in myprocess for producing the novel compounds of my invention by using smallor catalytic amounts of boron-trifiuoride or pxylenesulfonic acidcatalyst in the reaction mixture. It was surprising to discover thesecatalysts since other acidic catalysts were found to be unsatisfactory.Catalytic amounts of boron trifiuoride or p-xylenesulfonic acid rangingfrom about 0.05 to about 0.5% or based on the weight of the nitroalcoholcan generally be utilized but boron trifiuoride is preferred. However,if desired, more or less than this amount can be used. In utilizing theboron trifiuoride catalyst in my process, I prefer to form a complexwith a compound inert to the reactants and the reaction products, forexample, an ether. Representative ethers which I have found to be usefulin forming complexes with boron trifiuoride include isopropyl ether,dimethyl ether, diethyl ether, dibutyl ether, and the like. I prefer acomplex of boron trifiuoride-diethyl ether containing about 45 to about50% by weight of boron trifiuoride based on the weight of the complex.Although free boron trifiuoride is a suitable catalyst in my process,its complexes with the ethers aforenamed are much easier to handle, useand store under ordinary industrial conditions, thus making thempreferable to free boron trifiuoride.

The molecular proportions used in producing the new compounds of myinvention can vary considerably depending on the nitroalcohol andepoxide used and/ or on the final product desired. Ordinarily, moleratios of nitroalcohol to epoxide of not less than 121 and not more thanabout 1:10 or 1:20 are useful in my process.

The epoxides from which I prepare my compounds must contain at least onegrouping. Representative epoxides include alkylene oxides such asethylene oxide, butene-l-oxide, isobutylene oxide, butadiene monoxide,1,2-epoxyoctane, 1,2-epoxytetradecane, 3,4 epoxy 1 butanol,1,2-epoxynonadecane, etc.; alkylene dioxides such as butadiene dioxide,etc.; halosubstituted alkylene oxides such as chloropropylene oxide,bromo propylene oxide, etc.; phenyl-substituted alkylene oxides such as1,2epoxyethylbenzenes, 1,2-epoxyoctylben zene,1,2-epoxyheptadecylbenzene, etc.; nitro-substituted phenyl-substitutedalkylene oxides such as 1,2-e oxyethylnitrobenzene, etc.;halo-substituted phenyl-substituted alkylene oxides such as 1,2-epoxychlorobenzene, styrene oxide, and the like.

The novel nitro compounds of my invention can be reduced by any suitablereducing procedure to the corresponding amines. Thus, the method of theinvention provides a novel and efficient means for obtaining novelaminohydroxyethers, compounds B, having the general formula:

present invention could be produced by oxyalkylating the.

novel nitro compounds to the corresponding novel amine compounds of thepresent invention. Because the amino compounds of the present inventionare more stable and 4. can be titrated, the structures of the nitrocompounds are more easily determined in terms of the structures of thecorresponding amino compounds.

In another aspect, the method of my invention affords the production ofa novel group of aminohydroxyethers having the structural formula thatcorresponds to that of the novel amino compounds given above forcompounds B with the proviso that only one of the R s in the formula isan alkyl group and R is the radical wherein R and y have the same valuesassigned above. In other words, the novel subgroup of aminohydroxyethersof the invention can be basically classified into three groups:

wherein R in each case is an alkyl group of up to 20 carbon atoms and RR and x have the values assigned above,

The same formula wherein only one of the R s is an alkyl group and theother is lower hydroxyalkyl, and R is the radical R1-O-CH2CHOHOH2OCH2-%1R1 OH ()H NH:

wherein R has the value assigned above; and

(III) The same formula as above wherein one R is alkyl, the other ishydroxyalkyl and R is the radical [OCH2-CH-] OH-- where R and y have thesame values assigned above.

The preparation of the aminohydroxyethers of I is effected byoxyalkylating the corresponding dialkyl nitro alcohols with any of theoxyalkylating agents described above in molar ratios also describedabove, followed by reduction of the nitro group of the resultingnitrohydroxyether to the amino group. The aminohydroxyethers of II onthe other hand can be prepared by oxyalkylating the monoalkyl aminoalcohols with butadiene dioxide in a mole ratio of alcohol to butadienedioxide of 2:1 and reducing the two nitro groups of the resulting nitrocompound to amine groups. The aminohydroxyethers of III can be similarlyprepared using an hydroxyalkyl, alkyl, nitroalkanol.

In carrying out the reduction step, I prefer to first neutralize anyremaining catalyst with a base, such as calcium hydroxide, and thendissolve the nitro compound in methanol and hydrogenate it underhydrogenation conditions, for instance, at temperatures ranging fromabout 25 C. to C. and at :a pressure of from about 400 to 500 psi. inthe presence of catalytic amounts of a nitro to amine reducing agent,e.g. a nickel catalyst such as Raney nickel catalyst. After thereduction has taken place, the amine can then be purified by anysuitable means, such as distillation.

The new nitrogen, i.e. nitro and aminohydroxyether compounds of theinvention, is useful as corrosion inhibitors, bactericides, pigmentwetting and dispersing agents, emulsifiers and as intermediates in thepreparation of nonionic surface active agents. For example, in utilizingeither the nitro or aminohydroxyethers as pigment wetting agents in apigment system, I can add from about 2% to 8% by weight based on theweight of the pigment system of the compounds to a pigment systemcontaining skilled in the art to be included within the scope of myinvention.

Example I To a closed reactor equipped with an agitator containing 1071grams of 2-nitro-2-methyl-l-propanol, having a temperature of 90 C.,were added milliliters of boron trifluoride-diethyl ether. Ethyleneoxide was then added from a cylinder into the reactor at a pressurebetweenl and 5 psi. over a period of approximately 7 hours during whichtime the temperature of the reaction never exceeded 130 C. Anoxyalkylated product containing 2-methyl-2-nitro-4-oxa-6-hydroxy hexanewas thereby produced. Y I grams of calcium hydroxide were then added tothe reaction mixture and the mixture was thoroughly agitated. Threeliters of methanol were then added to the mixture to form a slurry andthe slurry was filtered. To the filtrate were then added 100 grams ofR-aney nickel and the thus-treated filtrate was hydrogenated at apressure of approximately 400 to 500 psi. at an initial temperature ofC. As the reduction proceeded, the temperature was gradually increasedto approximately C. The hydrogenation required a period of about 2hours, during which time the reaction mixture was constantly agitated.After absorption of hydrogen had ceased, the reaction mixture waswithdrawn from the container, the catalyst removed from the solution byfiltration and the methanol separated from the reaction mixture by meansof fractional distillation. The residue thus obtained was subjected tofractional distillation under vacuum.2-methyI-G-hydroxy-4-oxa-2-hexylamine in the amount of 100 grams wascollected.

The following data was determined for the compound:

Found: N, 10.51%; H, 11.18%; C, 53.45%. Calculated: N, 10.5%; H, 11.3%;C, 54.1%.

Example II One mole of 2-nitro-2-methyl-l-propanol is reacted with twomoles of 1,2-epoxyethylbenzene in accordance with the general procedureof Example I to produce 2- methyl-Z-nitro-4J dioxa-6,9-diphenyl9-hydroxynonane. This nitro compound is reduced as in Example I to obtain 2methyl-9-hydroxy-4,7-dioxa-6,9 diphenyl-Z-nonylamine.

Example III One mole of 2-nitro-2-rnethyl-l-propanol is reacted one moleof 1,2-epoxyoctylbenzene in accordance with the general procedure ofExample I to produce Z-methyl- 2-nitro-4-oxa-6-hexylphenyl-6 -hydroxyhexane. This nitro compound is reduced as in Example I to obtainZ-methyl- 6-hydroxy-4-oxa-6-hexylphenyl-2-hexylamine.

Example IV One mole of 2-nitro-2-methyl-l-propanol is reacted with twomoles of 1,2-epoxyheptadecane in accordance with the general procedureof Example 1 to produce Z-methyl- 2-nitr0-4,7 dioxa-6,9dipentadecyl-9-hydroxy nonane. This nitro compound is reduced as inExample I to obtain 2-methyl-9-hydroxy-4,7 dioxa-6 ,9- dipentadecy1-2-nonylamine. 1

Example V One mole of 2-nitro-2-methyl-l-propanol is reacted with onemole of chloropropylene oxide in accordance with the general procedureof Example I to produce 2- methyl-Z-nitro-6-hydroxy-4-oxa-6 chloromethylhexane. This nitro compound is reduced as in Example I to obtainZ-methyl-6-hydroxy-4-oxa-6-chloromethyl-2 hexylamine.

ExampleVI One mole of 2-nitro-2-methyl-l-propanol is reacted with twomoles of 1,2-epoxyheptadecylbenzene in accordance with the generalprocedure of Example I to produce 2- methyl 2-nitro-4,7-dioxa6,9-di(phenyl pentadecyl)-9- hydroxy nonane. This nitro compound isreduced as in Example I to obtain 2-methyl-9-hydroxy-4,7-dioxa-6,9-di-(phenyl pentadecyl)-2-nonylarnine.

Example VII Two moles of Z-nitrO-Z-methyl-l-p-ropanol is reacted withone mole of butadiene dioxide in accordance with the general procedureof Example I to produce 2,11-dimethyl-2,11dinitro-4,9-dioxa-6,7-dihydroxy dodecane. This nitro compound is reducedas in Example I to obtain 2,11 dimethyl-6,7-dihydroxy-4,9-dioxa2,11-dodecanediamine.

Example VIII One mole of 2-nitro-2-methyl-l-propanol is reacted with onemole of 1,2-epoxyethyl nitrobenzene in accordance with the generalprocedure of Example I to produce 2-methyl-2-nitro-4-oxa-6-nitrophenyl-6hydroxy hexane. This nitro compound is reduced as in Example I to obtain2-methyl-6-hydroxy-4-oxa-6-nitrophenyl-2 hexylamine.

Example Di One mole of 2-nitro-2-methyl-l-propanol is reacted with twomoles of propylene oxide in accordance with the general procedure ofExample I to produce 2-methyl- 2-nitro-4,7-dioxa-6,9-dimethyl-9-hydroxynonane. This nitro compound is reduced as in Example I to obtain 2-methyl-9-hydr0xy-4,7-dioxa-6,9-dimethyl-2-nonylamine.

Example X One mole of 3-methyl-3-nitro-2-butanol is reacted with onemole of ethylene oxide in accordance with the general procedure ofExample I to produce 2,3-dimethyl-2- nitro-4-oxa-6-hydroxyhexane. Thisnitro compound is reduced as in Example I to obtain2,3-dimethyl-6-hydroxy- 4-oxa-2-hexylamine.

Example XI One mole of 2-nitro-2-methyl-l-hexanol is reacted with onemole of ethylene oxide in accordance with the general procedure ofExample I to produce S-methyl-S-nitro- 3-oxa-l-nonyl alcohol. This nitrocompound is reduced as in Example I to obtain 5amino-5-methyl-3-oxa-1-nonyl alcohol.

Example XII One mole of 2-nitro-2-methyl-l-nonadecanol is reacted withone mole of ethylene oxide in accordance with the general procedure ofExample I to produce 18-methyl-l8- nitro-20-oxa-22-hydroxy docosane.This nitro compound is reduced as in Example I to obtain18-methyl-22-hydroxy-20-oxa-18-docosylamine.

Example XIII One mole of 12-nitro-12-methyl-1-tridecanol is reacted withone mole of ethylene oxide in accordance with the general procedure ofExample I to produce 2-methy1-2- nitro-14-oxa-16-hydroxyhexadecane. Thenitro compound is then reduced as in Example I to obtain 2-methyl-14-oxa-l6-hydroxy-2-hexadecylamine.

Example XIV One mole of 6-nitro-6-ethyl-1-heptanol is reacted with onemole of ethylene oxide as in Example I to produce2-ethy1-2-nitro-8-oxa-IO-hydroxy decane. This nitro compound is reducedas in Example I to obtain 2-ethyl-l0-hydroxy-8-oxa-2-decylamine.

7 Example XV One mole of 2-nitro-2-methyl-l-propanol is reacted with 16moles of ethylene oxide to produce 2-methyl-2- nitro4,7,10,13,16,19,22,25,28,31,34,37,40,43,46,49-hexadeca-oxa-Sl-hydroxy-dopentacontane.This compound is reduced as in Example I to :obtain Z-methyl-Sl-hydroxy-4,7,10,13,l6,19,22,25,28,3l,34,37,40,43,46,49hexadecaoxa-2-dopentacontanylamine.

Example XVI One mole of tris(hydroxymethyl)nitromethane is reacted withthree moles of ethylene oxide in accordance with the general procedureof Example I to produce tris- (Z-hydroxyethoxy-methyl)nitromethane. Thecompound is reduced as in Example I to obtaintris(2-hydroxyethoxymethyl)met-hylamine.

Example XVII One mole of tris(hydroxyethyl)nitromethane and three molesof ethylene oxide are reacted following the procedure of Example I togive tris(2-hydroxyethoxy-ethyl)- nitromethane. The compound is reducedas in Example I to obtain tris (2-hydroxyethoxy-ethyl) methylamine.

Example XVIII Reaction of one mole of tris(hydroxyethyl)nitromethanewith 2 moles of ethylene oxide following the procedure of Example Iprovides di(2-hydroxyethoxy-ethyl)- hydroxyethyl nitromethane. Reductionof this compound as in Example I provides the corresponding amine.

Example XIX One mole of 2-nitro-2-methyl-l-propanol is reacted with onemole of 1,Z-epoxyethyl-p-chlorobenzene in accordance with the procedureof Example I to produce 2-methyl-2-nitro-4-oxa-6-p-chlorophenyl-6-hydroxy hexane. This nitrocompound is reduced as in Example I to obtain2-methyl-6-hydroxy-4-oxa-6-p-chlorophenyl-2-hexylamine.

Example XX One mole of 2-nitro-2-methyl-l-propanol is reacted with onemole of butadiene monoxide in accordance with the procedure set forth inExample I to produce 2-nitro- 2-methyl-4-oxa-6-hydroxy-6-vinyl hexane.This nitro compound is reduced as in Example I to provide 2-methyl-4-oxa-6-hydr-oxy-6-vinyl-2-hexylamine.

Example XXI One mole of 2-nitro-2-methyl-l-propanol is reacted with onemole of styrene oxide using 1.2 percent of pxylenesulfonic acid ascatalyst instead of the boron trifluoride to produce2-nitro-2-methyl-4-oxa-6-phenyl-6-hydroxy hexane which is reduced as inExample I to provide 2-methyl-4-oxa-6-phenyl-6-hydroxy hexylamine.

Example XXII One mole of 2-nitro-2-methyl-l-propanol is reacted with onemole of 3,4-epoxy-1-butanol in accordance with the procedure of ExampleI to :produce 2-nitro-2-methyl- 4-0xa-6-hydroxy-6-hydroxyethyl hexanewhich is reduced as in Example I to provide 2-methyl-4-oxa-6-hydroxy-6-hydroxyethyl-Z-hexylamine.

Example XXIII To a closed reactor equipped with an agitator containing asolution of 302 grams of tris(hydroxymethyl)nitromethane in 300 grams ofisopropyl ether was added 1 milliliter of boron trifluoride-diethylether to form a reaction mixture. The reaction mixture was heated toabout 37 C. Ethylene oxide was then added from a cylinder into thereactor at a pressure between 1 and 2 /2 p.s.i. over a period ofapproximately 11 hours during which time the temperature of the reactionnever exceeded 75 C. At the completion of the 11 hour period theresulting material was heated under vacuum at about 50 C. to remove theisopropyl ether. Tris(Z-hydroxyethoxy-methyl)nitromethane in the amountof 583 grams was obtained.

The following data were determined for the compound: Found: N (Dumas),4.89%. Calculated: N, 4.8%.

Example XXIV The following is a stabilized steam cylinder oil which isadequately protected against bacteria by the addition oftris(Z-hydroxyethoxy-methyl) nitromet-hane.

Percent by weight S.A.E. lubricating oil 90 Oleic acid 10 Example XXVThe following is a core oil which is adequately protected againstbacteria by the addition of tris(2-hydroxyethoxy-methyl) nitromethane.

Percent by weight Crude tall oil 25 Fuel oil 35 Tall oil ester 40Exam-pie XXVI The following is a cutting oil which is adequatelyprotected by the addition of the nitrohydroxyethers of the presentinvention.

Percent by weight Tallow Parafiin wax 29 Beeswax 1.3 Oxalic acid 1.3Potassium citrate 1.3 Urea .4

Generically, the novel compounds of the present invention can berepresented by the formula wherein R is a member selected from the groupconsisting of methyl and hydrogen; wherein R is a member selected fromthe group consisting of alkyl radicals of about 1 to 20 carbons atoms;lower hydroxyalkyl radicals; and a radical having the general formula:

R is a member selected from the group consisting of the radicals:

and

R1 O-CHg-CH-CH-OHz-O-CHz--Jh OH OH NO:

wherein R is methyl; R is chloromethyl; y is an integer ranging from 1to 20,

2. 2-methy1-2-nitro-6-hyd2 xy-4-oxa 6 chloromethyl- OTHER R EQERENCEShexane' Lambert et al., Jour. Chem. Soc. (1947), pp. 1474- ReferencesCited 1477' UNITED STATES PATENTS 5 LEON ZITVER, Primary Examiner. Re.26,069 8/1966 Fl'ump 260-615 XR H, MARS, Assistant Examiner.

2,483,739 10/1949 Roach et a1. 260-615 U.S. DEPARTMENT OF COMMERCEPATENT OFFICE Washington, 0.6. 20231 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No 3,402 ,206 September 17 1968 John A.Frump It is certified that error appears in the above identified patentand that said Letters Patent are hereby corrected as shown below: Column2, lines 38 to 42, the left-hand portion of the formu] should appear asshown below:

Column 5, line 54, after "reacted" insert with Signed and sealed this3rd day of February 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, IR.

Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

